Process And Device For Treating High Sulfur Heavy Marine Fuel Oil For Use As Feedstock In A Subsequent Refinery Unit

ABSTRACT

A multi-stage process for transforming a high sulfur ISO 8217 compliant Feedstock Heavy Marine Fuel Oil involving a core desulfurizing process that produces a Product Heavy Marine Fuel Oil that can be used as a feedstock for subsequent refinery process such as anode grade coking, needle coking and fluid catalytic cracking. The Product Heavy Marine Fuel Oil exhibits multiple properties desirable as a feedstock for those processes including a sulfur level has a maximum sulfur content (ISO 14596 or ISO 8754) between the range of 0.05 mass % to 1.0 mass. A process plant for conducting the process is also disclosed.

This application is a continuation of co-pending U.S. application Ser.No. 16/681,093, filed 12 Nov. 2019; U.S. application Ser. No. 16/681,093is a continuation of U.S. application Ser. No. 16/103,897, filed 14 Aug.2018, now U.S. patent Ser. No. 10/533,141, granted 14 Jan. 2020; U.S.application Ser. No. 16/103,897 is a continuation-in-part of ApplicationNo. PCT/US2018/017863, filed 12 Feb. 2018 now expired, Application No.PCT/US2018/017863 claims priority to U.S. Provisional Application No.62/589,479, filed 21 Nov. 2017, now expired, and Application No.PCT/US2018/017863 also claims priority to U.S. Provisional ApplicationNo. 62/458,002, filed 12 Feb. 2017, now expired; U.S. application Ser.No. 16/103,897 is also a continuation-in-part of Application No.PCT/US2018/017855, filed 12 Feb. 2018 now expired, Application No.PCT/US2018/017855 claims priority to U.S. Provisional Application No.62/589,479, filed 21 Nov. 2017, now expired, and Application No.PCT/US2018/017855 also claims priority to U.S. Provisional ApplicationNo. 62/458,002, filed 12 Feb. 2017, now expired, the entire contents ofeach of the recited foregoing applications being incorporated herein intheir entirety.

BACKGROUND

There are two basic marine fuel types: distillate based marine fuel,also known as Marine Gas Oil (MGO) or Marine Diesel Oil (MDO); andresidual based marine fuel, also known as heavy marine fuel oil (HMFO).Distillate based marine fuel both MGO and MDO, comprises petroleummiddle distillate fractions separated from crude oil in a refinery via adistillation process. Gasoil (also known as medium diesel) is apetroleum middle distillate in boiling range and viscosity betweenkerosene (light distillate) and lubricating oil (heavy distillate)containing a mixture of C₁₀ to C₁₉ hydrocarbons. Gasoil (a heavydistillate) is used to heat homes and is used blending with lightermiddle distillates as a fuel for heavy equipment such as cranes,bulldozers, generators, bobcats, tractors and combine harvesters.Generally maximizing middle distillate recovery from heavy distillatesmixed with petroleum residues is the most economic use of thesematerials by refiners because they can crack gas oils into valuablegasoline and distillates in a fluid catalytic cracking (FCC) unit.Diesel oils for road use are very similar to gas oils with road usediesel containing predominantly contain a middle distillate mixture ofC₁₀ through C₁₉ hydrocarbons, which include approximately 64% aliphatichydrocarbons, 1-2% olefinic hydrocarbons, and 35% aromatic hydrocarbons.Distillate based marine fuels (MDO and MGO) are essentially road dieselor gas oil fractions blended with up to 15% residual process streams,and optionally up to 5% volume of polycyclic aromatic hydrocarbons(asphaltenes). The residual and asphaltene materials are blended intothe middle distillate to form MDO and MGO as a way to both swell volumeand productively use these low value materials.

Asphaltenes are large and complex polycyclic hydrocarbons with apropensity to form complex and waxy precipitates, especially in thepresence of aliphatic (paraffinic) hydrocarbons that are the primarycomponent of Marine Diesel. Once asphaltenes have precipitated out, theyare notoriously difficult to re-dissolve and are described as fuel tanksludge in the marine shipping industry and marine bunker fuelingindustry. One of skill in the art will appreciate that mixing MarineDiesel with asphaltenes and process residues is limited by thecompatibility of the materials and formation of asphaltene precipitatesand the minimum Cetane number required for such fuels.

Residual based fuels or Heavy Marine Fuel Oil (HMFO) are used by largeocean-going ships as fuel for large two stroke diesel engines for over50 years. HMFO is a blend of the residues generated throughout the crudeoil refinery process. Typical refinery streams combined to from HMFO mayinclude, but are not limited to: atmospheric tower bottoms (i.e.atmospheric residues), vacuum tower bottoms (i.e. vacuum residues)visbreaker residue, FCC Light Cycle Oil (LCO), FCC Heavy Cycle Oil (HCO)also known as FCC bottoms, FCC Slurry Oil, heavy gas oils and delayedcracker oil (DCO), deasphalted oils (DAO); heavy aromatic residues andmixtures of polycyclic aromatic hydrocarbons, reclaimed land transportmotor oils; pyrolysis oils and tars; aspahltene solids and tars; andminor portions (often less than 20% vol.) of middle distillate materialssuch as cutter oil, kerosene or diesel to achieve a desired viscosity.HMFO has a higher aromatic content (especially polynuclear aromatics andasphaltenes) than the marine distillate fuels noted above. The HMFOcomponent mixture varies widely depending upon the crude slate (i.e.source of crude oil) processed by a refinery and the processes utilizedwithin that refinery to extract the most value out of a barrel of crudeoil. The HMFO is generally characterized as being highly viscous, highin sulfur and metal content (up to 5 wt %), and high in asphaltenesmaking HMFO the one product of the refining process that hashistorically had a per barrel value less than feedstock crude oil.

Industry statistics indicate that about 90% of the HMFO sold contains3.5 weight % sulfur. With an estimated total worldwide consumption ofHMFO of approximately 300 million tons per year, the annual productionof sulfur dioxide by the shipping industry is estimated to be over 21million tons per year. Emissions from HMFO burning in ships contributesignificantly to both global marine air pollution and local marine airpollution levels.

The International Convention for the Prevention of Pollution from Ships,also known as the MARPOL convention or just MARPOL, as administered bythe International Maritime Organization (IMO) was enacted to preventmarine pollution (i.e. marpol) from ships. In 1997, a new annex wasadded to the MARPOL convention; the Regulations for the Prevention ofAir Pollution from Ships—Annex VI to minimize airborne emissions fromships (SO_(x), NO_(x), ODS, VOC) and their contribution to global airpollution. A revised Annex VI with tightened emissions limits wasadopted in October 2008 and effective 1 Jul. 2010 (hereafter calledAnnex VI (revised) or simply Annex VI).

MARPOL Annex VI (revised) adopted in 2008 established a set of stringentair emissions limits for all vessel and more specifically designatedEmission Control Areas (ECAs). The ECAs under MARPOL Annex VI are: i)Baltic Sea area—as defined in Annex I of MARPOL—SO_(x), only; ii) NorthSea area—as defined in Annex V of MARPOL—SO_(x), only; iii) NorthAmerican—as defined in Appendix VII of Annex VI of MARPOL—SO_(x),NO_(x), and PM; and, iv) United States Caribbean Sea area—as defined inAppendix VII of Annex VI of MARPOL—SO_(x), NO_(x) and PM.

Annex VI (revised) was codified in the United States by the Act toPrevent Pollution from Ships (APPS). Under the authority of APPS, theU.S. Environmental Protection Agency (the EPA), in consultation with theUnited States Coast Guard (USCG), promulgated regulations whichincorporate by reference the full text of Annex VI. See 40 C.F.R. §1043.100(a)(1). On Aug. 1, 2012 the maximum sulfur content of all marinefuel oils used onboard ships operating in US waters/ECA was reduced from3.5% wt. to 1.00% wt. (10,000 ppm) and on Jan. 1, 2015 the maximumsulfur content of all marine fuel oils used in the North American ECAwas lowered to 0.10% wt. (1,000 ppm). At the time of implementation, theUnited States government indicated that vessel operators must vigorouslyprepare to comply with the 0.10% wt. (1,000 ppm) US ECA marine fuel oilsulfur standard. To encourage compliance, the EPA and USCG refused toconsider the cost of compliant low sulfur fuel oil to be a valid basisfor claiming that compliant fuel oil was not available for purchase. Forover five years there has been a very strong economic incentive to meetthe marine industry demands for low sulfur HMFO, however technicallyviable solutions have not been realized and a premium price has beencommanded by refiners to supply a low sulfur HMFO compliant with AnnexVI sulfur emissions requirements in the ECA areas.

Since enactment in 2010, the global sulfur cap for HMFO outside of theECA areas was set by Annex VI at 3.50% wt. effective 1 Jan. 2012; with afurther reduction to 0.50% wt, effective 1 Jan. 2020. The global cap onsulfur content in HMFO has been the subject of much discussion in boththe marine shipping and marine fuel bunkering industry. There has beenand continues to be a very strong economic incentive to meet theinternational marine industry demands for low sulfur HMFO (i.e. HMFOwith a sulfur content less than 0.50 wt. %. Notwithstanding this globaldemand, solutions for transforming high sulfur HMFO into low sulfur HMFOhave not been realized or brought to market. There is an on-going andurgent demand for processes and methods for making a low sulfur HMFOcompliant with MARPOL Annex VI emissions requirements.

Replacement of heavy marine fuel oil with marine gas oil or marinediesel: One primary solution to the demand for low sulfur HMFO to simplyreplace high sulfur HMFO with marine gas oil (MGO) or marine diesel(MDO). The first major difficulty is the constraint in global supply ofmiddle distillate materials that make up 85-90% vol of MGO and MDO. Itis reported that the effective spare capacity to produce MGO is lessthan 100 million metric tons per year resulting in an annual shortfallin marine fuel of over 200 million metric tons per year. Refiners notonly lack the capacity to increase the production of MGO, but they haveno economic motivation because higher value and higher margins can beobtained from using middle distillate fractions for low sulfur dieselfuel for land-based transportation systems (i.e. trucks, trains, masstransit systems, heavy construction equipment, etc.).

Processing of residual oils. For the past several decades, the focus ofrefining industry research efforts related to the processing of heavyoils (crude oils, distressed oils, or residual oils) has been onupgrading the properties of these low value refinery process oils tocreate middle distillate and lighter oils with greater value. Thechallenge has been that crude oil, distressed oil and residues containhigh levels of sulfur, nitrogen, phosphorous, metals (especiallyvanadium and nickel); asphaltenes and thus exhibit a propensity to formcarbon or coke on the catalyst. The sulfur and nitrogen molecules arehighly refractory and aromatically stable and thus difficult andexpensive to crack or remove. Vanadium and nickel porphyrins and othermetal organic compounds are responsible for catalyst contamination andcorrosion problems in the refinery. The sulfur, nitrogen, andphosphorous, must be removed because they are well-known poisons for theprecious metal (platinum and palladium) catalysts utilized in theprocesses downstream of the atmospheric or vacuum distillation towers.

The difficulties treating atmospheric or vacuum residual streams hasbeen known for many years and has been the subject of considerableresearch and investigation. Numerous residue-oil conversion processeshave been developed in which the goals are same: 1) create a morevaluable, preferably middle distillate range hydrocarbons; and 2)concentrate the contaminates such as sulfur, nitrogen, phosphorous,metals and asphaltenes into a form (coke, heavy coker residue, FCCslurry oil) for removal from the refinery stream. Well known andaccepted practice in the refining industry is to increase the reactionseverity (elevated temperature and pressure) to produce hydrocarbonproducts that are lighter and more purified, increase catalyst lifetimes and remove sulfur, nitrogen, phosphorous, metals and asphaltenesfrom the refinery stream.

In summary, since the announcement of the MARPOL Annex VI standardsreducing the global levels of sulfur in HMFO, refiners of crude oil havehad modest success in their technical efforts to re-purpose high sulfurHMFO. With demand for high sulfur HMFO decreasing and the use of lowsulfur alternatives in the marine industry, there exists a long standingand unmet need for processes and devices that transform high sulfur HMFOfor use as a feedstock to other subsequent refinery processes.

SUMMARY

It is a general objective to transform high sulfur a Heavy Marine FuelOil (HMFO) in a multi stage process that minimizes the changes in thedesirable feed properties of the HMFO and minimizes the production ofby-product hydrocarbons (i.e. light hydrocarbons having C₁-C₄ and wildnaphtha (C₅-C₂₀)).

A first aspect and illustrative embodiment encompasses a multi-stageprocess for treating high sulfur Heavy Marine Fuel Oil for use asfeedstock in a subsequent refinery unit, the process involving: mixing aquantity of the Feedstock Heavy Marine Fuel Oil with a quantity ofActivating Gas mixture to give a Feedstock Mixture; contacting theFeedstock Mixture with one or more catalysts under reactive conditionsto form a Process Mixture from the Feedstock Mixture; receiving theProcess Mixture and separating the Product Heavy Marine Fuel Oil liquidcomponents of the Process Mixture from the gaseous components andby-product hydrocarbon components of the Process Mixture and,discharging the Product Heavy Marine Fuel Oil.

A second aspect and illustrative embodiment encompasses a device orplant for treating high sulfur Heavy Marine Fuel Oil and producing aProduct HMFO for use as feedstock in a subsequent refinery unit. Theillustrative devices embody the above illustrative core processes on acommercial scale.

A third aspect and illustrative embodiment encompasses a feedstock HeavyMarine Fuel Oil composition resulting from the above illustrativeprocesses and devices.

DESCRIPTION OF DRAWINGS

FIG. 1 is a process block flow diagram of an illustrative core processto produce Product HMFO.

FIG. 2 is a process flow diagram of a multistage process fortransforming the high sulfur Feedstock HMFO to produce Product HMFO.

FIG. 3 is a process flow diagram of a first alternative configurationfor the reactor Section (11) for the process in FIG. 2 .

FIG. 4 is a process flow diagram of a second alternative configurationfor the reactor Section (11) for the process in FIG. 2 .

FIG. 5 is a process flow diagram of a third alternative multi-reactorconfiguration for the Reactor System (11) in FIG. 2 .

FIG. 6 is a process flow diagram of a fourth alternative multi-reactormatrix configuration for the Reactor System (11) in FIG. 2 .

DETAILED DESCRIPTION

The inventive concepts as described herein utilize terms that should bewell known to one of skill in the art, however certain terms areutilized having a specific intended meaning and these terms are definedbelow:

Heavy Marine Fuel Oil (HMFO) is a petroleum product fuel compliant withthe ISO 8217 (2017) standards for residual marine fuels except for theconcentration levels of the Environmental Contaminates.

Environmental Contaminates are organic and inorganic components of HMFOthat result in the formation of SO_(x), NO_(x) and particulate materialsupon combustion.

Feedstock HMFO is a petroleum product fuel compliant with the ISO 8217(2017) standards for the physical properties or characteristics of amerchantable HMFO except for the concentration of EnvironmentalContaminates, more specifically the Feedstock HMFO has a sulfur contentgreater than the global MARPOL Annex VI standard of 0.5% wt. sulfur, andpreferably and has a sulfur content (ISO 14596 or ISO 8754) between therange of 5.0% wt. to 1.0% wt.

Product HMFO is a petroleum product fuel that has a maximum sulfurcontent (ISO 14596 or ISO 8754) between the range of 0.05% wt. to 1.0%wt. and is suitable for use as a feedstock in subsequent refineryprocess such Coking or Fluid Catalytic Cracking.

Activating Gas: is a mixture of gases utilized in the process combinedwith the catalyst to remove the environmental contaminates from theFeedstock HMFO.

Fluid communication: is the capability to transfer fluids (eitherliquid, gas or combinations thereof, which might have suspended solids)from a first vessel or location to a second vessel or location, this mayencompass connections made by pipes (also called a line), spools,valves, intermediate holding tanks or surge tanks (also called a drum).

Merchantable quality: is a level of quality for a residual marine fueloil so the fuel is fit for the ordinary purpose it should serve (i.e.serve as a residual fuel source for a marine ship) and can becommercially sold as and is fungible and compatible with other heavy orresidual marine bunker fuels.

Bbl or bbl: is a standard volumetric measure for oil; 1 bbl=0.1589873m³; or 1 bbl=158.9873 liters; or 1 bbl=42.00 US liquid gallons.

Bpd or bpd: is an abbreviation for Bbl per day.

SCF: is an abbreviation for standard cubic foot of a gas; a standardcubic foot (at 14.73 psi and 60° F.) equals 0.0283058557 standard cubicmeters (at 101.325 kPa and 15° C.).

Bulk Properties: are broadly defined as the physical properties orcharacteristics of a merchantable HMFO as required by ISO 8217 (2017);and more specifically the measurements include: kinematic viscosity at50° C. as determined by ISO 3104; density at 15° C. as determined by ISO3675; CCAI value as determined by ISO 8217, ANNEX B; flash point asdetermined by ISO 2719; total sediment—aged as determined by ISO10307-2; carbon residue—micro method as determined by ISO 10370; andpreferably aluminum plus silicon content as determined by ISO 10478.

The inventive concepts are illustrated in more detail in thisdescription referring to the drawings, in which FIG. 1 shows thegeneralized block process flows for a core process of transforming ahigh sulfur Feedstock HMFO and producing a Product HMFO that may beutilized in subsequent refinery process. A predetermined volume ofFeedstock HMFO (2) is mixed with a predetermined quantity of ActivatingGas (4) to give a Feedstock Mixture. The Feedstock HMFO utilizedgenerally complies with the bulk physical and certain key chemicalproperties for a residual marine fuel oil otherwise compliant with ISO8217 (2017) exclusive of the Environmental Contaminates. Moreparticularly, when the Environmental Contaminate is sulfur, theconcentration of sulfur in the Feedstock HMFO may be between the rangeof 5.0% wt. to 1.0% wt. The Feedstock HMFO should have bulk physicalproperties required of an ISO 8217 (2017) compliant HMFO. The FeedstockHMFO should exhibit the Bulk Properties of: a maximum of kinematicviscosity at 50° C. (ISO 3104) between the range from 180 mm²/s to 700mm²/s; a maximum of density at 15° C. (ISO 3675) between the range of991.0 kg/m³ to 1010.0 kg/m³; a CCAI in the range of 780 to 870; and aflash point (ISO 2719) no lower than 60° C. Environmental Contaminatesother than sulfur that may be present in the Feedstock HMFO over the ISOrequirements may include vanadium, nickel, iron, aluminum and siliconsubstantially reduced by the process of the present invention. However,one of skill in the art will appreciate that the vanadium content servesas a general indicator of these other Environmental Contaminates. In onepreferred embodiment the vanadium content is ISO compliant so theFeedstock HMFO has a maximum vanadium content (ISO 14597) between therange from 350 mg/kg to 450 ppm mg/kg.

As for the properties of the Activating Gas, the Activating Gas shouldbe selected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseouswater, and methane. The mixture of gases within the Activating Gasshould have an ideal gas partial pressure of hydrogen (p_(H2)) greaterthan 80% of the total pressure of the Activating Gas mixture (P) andmore preferably wherein the Activating Gas has an ideal gas partialpressure of hydrogen (p_(H2)) greater than 95% of the total pressure ofthe Activating Gas mixture (P). It will be appreciated by one of skillin the art that the molar content of the Activating Gas is anothercriterion the Activating Gas should have a hydrogen mole fraction in therange between 80% and 100% of the total moles of Activating Gas mixture.

The Feedstock Mixture (i.e. mixture of Feedstock HMFO and ActivatingGas) is brought up to the process conditions of temperature and pressureand introduced into a Reactor System, preferably a reactor vessel, sothe Feedstock Mixture is then contacted under reactive conditions withone or more catalysts (8) to form a Process Mixture from the FeedstockMixture.

The core process conditions are selected so the ratio of the quantity ofthe Activating Gas to the quantity of Feedstock HMFO is 250 scf gas/bblof Feedstock HMFO to 10,000 scf gas/bbl of Feedstock HMFO; andpreferably between 2000 scf gas/bbl of Feedstock HMFO 1 to 5000 scfgas/bbl of Feedstock HMFO more preferably between 2500 scf gas/bbl ofFeedstock HMFO to 4500 scf gas/bbl of Feedstock HMFO. The processconditions are selected so the total pressure in the first vessel isbetween of 250 psig and 3000 psig; preferably between 1000 psig and 2500psig, and more preferably between 1500 psig and 2200 psig. The processreactive conditions are selected so the indicated temperature within thefirst vessel is between of 500° F. to 900° F., preferably between 650°F. and 850° F. and more preferably between 680° F. and 800° F. Theprocess conditions are selected so the liquid hourly space velocitywithin the first vessel is between 0.05 oil/hour/m³ catalyst and 1.0oil/hour/m³ catalyst; preferably between 0.08 oil/hour/m³ catalyst and0.5 oil/hour/m³ catalyst; and more preferably between 0.1 oil/hour/m³catalyst and 0.3 oil/hour/m³ catalyst to achieve deep desulfurizationwith product sulfur levels below 0.1 ppmw.

One of skill in the art will appreciate that the core process reactiveconditions are determined considering the hydraulic capacity of theunit. Exemplary hydraulic capacity for the treatment unit may be between100 bbl of Feedstock HMFO/day and 100,000 bbl of Feedstock HMFO/day,preferably between 1000 bbl of Feedstock HMFO/day and 60,000 bbl ofFeedstock HMFO/day, more preferably between 5,000 bbl of FeedstockHMFO/day and 45,000 bbl of Feedstock HMFO/day, and even more preferablybetween 10,000 bbl of Feedstock HMFO/day and 30,000 bbl of FeedstockHMFO/day.

One of skill in the art will appreciate that a fixed bed reactor using asupported transition metal heterogeneous catalyst will be thetechnically easiest to implement and is preferred. However, alternativereactor types may be utilized including, but not limited to: ebullatedor fluidized bed reactors; structured bed reactors; three-phase bubblereactors; reactive distillation bed reactors and the like all of whichmay be co-current or counter current. It is also contemplated that highflux or liquid full type reactors may be used such as those disclosed inU.S. Pat. Nos. 6,123,835; 6,428,686; 6,881,326; 7,291,257; 7,569,136 andother similar and related patents and patent applications.

The transition metal heterogeneous catalyst utilized comprises a porousinorganic oxide catalyst carrier and a transition metal catalytic metal.The porous inorganic oxide catalyst carrier is at least one carrierselected from the group consisting of alumina, alumina/boria carrier, acarrier containing metal-containing aluminosilicate, alumina/phosphoruscarrier, alumina/alkaline earth metal compound carrier, alumina/titaniacarrier and alumina/zirconia carrier. The transition metal catalyticmetal component of the catalyst is one or more metals selected from thegroup consisting of group 6, 8, 9 and 10 of the Periodic Table. In apreferred and illustrative embodiment, the transition metalheterogeneous catalyst is a porous inorganic oxide catalyst carrier anda transition metal catalyst, in which the preferred porous inorganicoxide catalyst carrier is alumina and the preferred transition metalcatalyst is Ni—Mo, Co—Mo, Ni—W or Ni—Co—Mo. The process by which thetransition metal heterogeneous catalyst is manufactured is known in theliterature and preferably the catalysts are commercially available ashydrodemetallization catalysts, transition catalysts, desulfurizationcatalyst and combinations of these which might be pre-sulfided.

The Process Mixture (10) in this core process is removed from theReactor System (8) and from being in contact with the one or morecatalyst and is sent via fluid communication to a second vessel (12),preferably a gas-liquid separator or hot separators and cold separators,for separating the liquid components (14) of the Process Mixture fromthe bulk gaseous components (16) of the Process Mixture. The gaseouscomponents (16) are treated beyond the battery limits of the immediateprocess. Such gaseous components may include a mixture of Activating Gascomponents and lighter hydrocarbons (mostly methane, ethane and propanebut some wild naphtha) that may have been formed as part of theby-product hydrocarbons from the process.

The Liquid Components (16) in this core process are sent via fluidcommunication to a third vessel (18), preferably a fuel oil productstripper system, for separating any residual gaseous components (20) andby-product hydrocarbon components (22) from the Product HMFO (24). Theresidual gaseous components (20) may be a mixture of gases selected fromthe group consisting of: nitrogen, hydrogen, carbon dioxide, hydrogensulfide, gaseous water, C₁-C₃ hydrocarbons. This residual gas is treatedoutside of the battery limits of the immediate process, combined withother gaseous components (16) removed from the Process Mixture (10) inthe second vessel (12). The liquid by-product hydrocarbon component,which are condensable hydrocarbons formed in the process (22) may be amixture selected from the group consisting of C₄-C₂₀ hydrocarbons (wildnaphtha) (naphtha—diesel) and other condensable light liquid (C₄-C₈)hydrocarbons that can be utilized as part of the motor fuel blendingpool or sold as gasoline and diesel blending components on the openmarket. It is also contemplated that a second draw (not shown) may beincluded to withdraw a distillate product, preferably a middle to heavydistillate. These liquid by-product hydrocarbons should be less than 15%wt., preferably less than 5% wt. and more preferably less than 3% wt. ofthe overall process mass balance.

The Product HMFO (24) resulting from the core process is discharged viafluid communication into storage tanks or for use beyond the batterylimits of the immediate core process. The Product HMFO complies with ISO8217 (2017) and has a maximum sulfur content (ISO 14596 or ISO 8754)between the range of 0.05 mass % to 1.0 mass % preferably a sulfurcontent (ISO 14596 or ISO 8754) between the range of 0.05 mass % ppm and0.7 mass % and more preferably a sulfur content (ISO 14596 or ISO 8754)between the range of 0.1 mass % and 0.5 mass %. The vanadium content ofthe Product HMFO is also ISO compliant with a maximum vanadium content(ISO 14597) between the range from 350 mg/kg to 450 ppm mg/kg,preferably a vanadium content (ISO 14597) between the range of 200 mg/kgand 300 mg/kg and more preferably a vanadium content (ISO 14597) lessthan 50 mg/kg.

The Product HFMO should have bulk physical properties that are ISO 8217(2017) compliant. The Product HMFO should exhibit Bulk Properties of: amaximum of kinematic viscosity at 50° C. (ISO 3104) between the rangefrom 180 mm²/s to 700 mm²/s; a maximum of density at 15° C. (ISO 3675)between the range of 991.0 kg/m³ to 1010.0 kg/m³; a CCAI value in therange of 780 to 870; a flash point (ISO 2719) no lower than 60.0° C.; atotal sediment—aged (ISO 10307-2) of less than 0.10 mass %; a carbonresidue—micro method (ISO 10370) lower than 20.00 mass %, and preferablyan aluminum plus silicon (ISO 10478) content of less than 60 mg/kg.

Relative to the Feedstock HMFO, the Product HMFO will have a sulfurcontent (ISO 14596 or ISO 8754) between 1% and 20% of the maximum sulfurcontent of the Feedstock HMFO. That is the sulfur content of the Productwill be reduced by about 80% or greater when compared to the FeedstockHMFO. Similarly, the vanadium content (ISO 14597) of the Product HMFO isbetween 1% and 20% of the maximum vanadium content of the FeedstockHMFO. One of skill in the art will appreciate that the above dataindicates a substantial reduction in sulfur and vanadium contentindicate a process having achieved a substantial reduction in theEnvironmental Contaminates from the Feedstock HMFO while maintaining thedesirable properties of an ISO 8217 (2017) compliant and merchantableHMFO.

As a side note, the residual gaseous component is a mixture of gasesselected from the group consisting of: nitrogen, hydrogen, carbondioxide, hydrogen sulfide, gaseous water, C₁-C₄ hydrocarbons. An aminescrubber will effectively remove the hydrogen sulfide content which canthen be processed using technologies and processes well known to one ofskill in the art. In one preferable illustrative embodiment, thehydrogen sulfide is converted into elemental sulfur using the well-knownClaus process. An alternative embodiment utilizes a proprietary processfor conversion of the Hydrogen sulfide to hydrosulfuric acid. Eitherway, the sulfur is removed from entering the environment prior tocombusting the HMFO in a ships engine. The cleaned gas can be vented,flared or more preferably recycled back for use as Activating Gas.

Pre and Post Process Units: It will be appreciated by one of skill inthe art, that the conditions utilized in the core process have beenintentionally selected to minimize cracking of hydrocarbons, but removesignificant levels of sulfur and other Environmental Contaminates fromthe Feedstock HMFO. However, one of skill in the art will alsoappreciate there may be certain compounds present in the Feedstock HMFOremoval of which would have a positive impact upon the subsequentprocess feedstock qualities of the Product HMFO. These processes andsystems must achieve this without substantially altering the subsequentprocess feedstock qualities of the Product HMFO. Process for the Pre andPost treatment of the HMFO in the above illustrative core process havebeen described in greater detail in co-owned patent applications. Thesepre- and post-process units may include, but are not limited to: removalof Detrimental Solids (such as catalyst fines); treatment with microwaveenergy; treatment with ultrasound energy; extraction of sulfur and otherpolar compounds with ionic liquids; absorption of sulfur andorganosulfur compounds on absorptive media; selective oxidation of theorganosulfur compounds, including the use of peroxides and ozone to formsulfones which can be subsequently removed; dewatering and desaltingunits; the use of guard beds to remove detrimental materials such asclays, ionic solids, particles, and the like; and combinations of these.

Product HMFO and Use as Feedstock The Product HFMO resulting from thedisclosed illustrative process may be used as a feedstock in subsequentrefinery process selected from the group including: anode grade cokingprocess unit, needle grade coking process unit and fluid catalyticcracking process unit. The Product HMFO has a sulfur content (ISO 14596or ISO 8754) less than 0.5 wt % and preferably less than 0.1% wt. andthus forms a low sulfur feedstock material that is useful in subsequentrefinery processes. That is the sulfur content of the Product HMFO hasbeen reduced by about 80% or greater when compared to the FeedstockHMFO. One of skill in the art will appreciate the Product Heavy MarineFuel Oil may be fractionated to remove a light to middle distillatefraction, said light to middle distillate fraction have a maximumboiling point less than 650° F., preferably less than 600° F. In thisway one can remove a valuable by-product light and middle distillatefraction prior to sending it to the subsequent refinery processes. Toillustrate and further explain the above inventive concepts examples ofusing the Product HMFO as a coker process unit feedstock and a fluidcatalytic cracking process feedstock are described below.

Product HMFO as Coker Feedstock: Coking is a severe thermal crackingprocess during which residual feedstocks are cracked to produce lighter,more valuable products and simultaneously produce a coke material ofdesired quality. A fired heater is used in the process to reach thermalcracking temperatures of 485° C. to 505° C. For a delayed coker, thecoking is delayed until the feed reaches the coking drums. The preheatedfeed in the tubes undergoes decomposition and condensation reactions andonce the feed reaches the drum, the condensation reactions between theliquids result in the formation of coke along with the evolution oflight gases and liquids.

The quality of the coke formed depends on the quality of the feed andthe temperature, pressure and the recycle ratio of the process.Typically there are three kinds of cokes that can be obtained in theprocess: anode grade (sponge) coke, shot coke and needle coke. Anodegrade coke is a porous solid which is used as a solid fuel or for theproduction of anodes for use in the aluminum industry. Shot coke is aless desirable coke occasionally produced along with sponge coke; itconsists of small hard spheres of low porosity and typically is used asfuel. Needle coke is premium quality coke, which is characterized by aneedle-like appearance and crystalline microstructure. The graphiteartifacts made from needle coke have a low coefficient of thermalexpansion and low electrical resistance and is used for makingelectrodes for use in the steel industry. The characteristics of thevarious cokes and their end use are presented below:

Type of Coke Characteristics End Use Anode Grade Sponge like appearance,higher Aluminum anodes, Coke surface area, lower TiO₂ pigmentscontaminant levels, higher volatile content, higher HGI (Hardgrovegrindabillity index) Shot Coke Spherical appearance, lower Coke ovens,surface area, lower volatiles, combustion lower HGI, tends toagglomerate Needle Coke Needlelike appearance, low Electrodes,volatiles, high carbon contents. Synthetic Graphite

One of skill in the art of coking will understand that key feedstockproperties that affect Coke Yield and Quality are: Gravity;Distillation; Conradson Carbon Residue; Asphaltene Content; Sulfur;Metals/Ash; Nitrogen; Hydrogen Content/Aromaticity. Typical FeedstockLimitations to produce Anode Grade Coke generally include, but are notlimited to: Sulfur: less than about 1.0 wt %; Vanadium: less than about100 ppmw and Nickel: less than about 100 ppmw. Typical FeedstockLimitations to produce Needle Coke generally include, but are notlimited to: Sulfur: in the range from about 0.0-0.7 wt %; Vanadium: lessthan about 50 ppmw; Nickel: less than about 50 ppmw; Aromatic Content:in the range from about 50-80 wt %; Asphaltene Content: less than about8 wt %; Nitrogen Content: in the range from about 0.0-0.7 wt; Ash: lessthan about 100 ppmw. It will be quickly realized by one of skill in theart that the Product HMFO has meets all of the requirements necessary tobe used as high quality coker feedstock, that is: low sulfur content(<1%), low vanadium content (typically <20 ppmw), low nickel content(typically <20 ppmw), high aromatics content (50-80%), low asphaltenecontent (<10%), low saturates content (<15%), micro carbon residue (MCR)content of 5-20% wt.

In a variation of the processes and devices disclosed above,specifically when a coker feedstock is the desired goal, certainmodifications can be made to enhance or optimize the Product HMFO as ahigh quality coker feedstock material. For example, the design of theProduct Stabilizer may be modified to take a distillate side cutproduct, to separate mid-boiling (<approximately 600 F) components fromthe Product HMFO Coker Feedstock. Alternatively, the separation ofdistillate product and Coker Feedstock can be achieved in a separatedistillation column. One of skill in the art will appreciate that thecutpoint between Coker Feedstock and distillate may be adjusted tooptimize coker performance. These modifications are well within thescope and skill of one in the art of refinery engineering and refineryprocess design.

Product HMFO as Fluid Catalytic Cracking Process Unit Feedstock: As theterm is used in this disclosure, Fluid Catalytic Cracking (FCC) isutilized as a generalized term to encompass both Fluid CatalyticCracking and Resid Fluid Catalytic Cracking processes.

The FCC Unit is the most common refinery unit used to upgrade heavierfractions to light products. The FCC cracks the feed material using heatin the presence of a catalyst. The primary product is FCC naphtha, whichis used in gasoline product blending. The FCC also produces lighterproducts and heavier products that can be blended into diesel andresidual fuel oil.

The FCC is particularly valuable in a refinery that is trying tomaximize gasoline production over residual fuel oil. The FCC yields ahigh volume of high quality naphtha (high octane and low vaporpressure). However, the diesel yield is low and of low quality, since itis made up of cracked material which tends to have low cetane.

The RFCC is a variant on the FCC. It is a similar unit yielding asimilar range and quality of products, but it is designed to handleheavier residual streams as a feed.

In the FCC Unit, heated feed is mixed with a heated catalyst andinjected into a reactor, where the catalyst freely mixes with the feedas a fluid. As the feed is cracked, coke deposits on the catalyst,causing it to gradually deactivate. Cracked product is drawn off at thetop of the reactor and is sent to a fractionator. Deactivated catalystis drawn off the bottom of the reactor and is sent to a regenerator,where the coke is burned off by injecting heat and air. The cleaned(regenerated) catalyst is then sent back to the reactor, and the cyclerepeats.

The catalyst moves around the reactor and regenerator circuits inseconds at very high velocities, so many internal surfaces on thecatalyst circuit must be protected against erosion by having ceramiccoatings. The heat generated in the regenerator from burning the cokeoff the catalyst provides the majority of the heat required for theseparation reactions taking place in the reactor, and the unit has to beheat-balanced between the reactor and regenerator. Coke burned off thecatalyst in the regenerator creates a mix of carbon monoxide and carbondioxide plus some SO_(x). This gas stream is passed through a carbonmonoxide boiler and recovery gas compressor to recover some energy, thencleaned of catalyst fines and evacuated to the atmosphere, so the FCC isa major emitter of carbon dioxide from refineries.

The FCC produces a range of mostly lighter products, with the mostsignificant being FCC gasoline. Typical products are: FCC naphtha—Thismaterial has octane and vapor pressure close to the qualityspecifications for finished gasoline. This is typically the largestproduct at around 50% of FCC output; Cycle oils—The FCC produces adiesel range product called cycle oil. This is highly aromatic, whichmakes it a poor diesel blendstock. It is typically blended into lowerquality diesel, used as a cutter stock in fuel oil blending, or sent tothe hydrocracker for upgrading; FCC slurry—The heaviest product from theFCC is a highly aromatic residual stream. This is sent for fuel oilblending, used as feed for the coker, or used to make specialty productssuch as carbon black or needle coke; FCC gas—The light ends from the FCCinclude both saturated and unsaturated hydrocarbons, such as C₃ and C₄hydrocarbons. Lighter gases (ethane and methane) are sent to a fuelsystem and utilized to power the refinery operations.

Upon review of the properties and characteristics of the Product HMFO,one of skill in the art will appreciate that the disclosed process anddevices improve the properties of a low value material in the form ofhigh sulfur Heavy Marine Fuel Oil (which preferably is ISO 8217 (2017)compliant) in a way which allow it to be used as FCC Unit feedstock.More specifically, the Product HMFO exhibits desirable properties of anFCC Unit feedstock that include: Sulfur Content below 0.5 wt % and morepreferably in the range of 0.1 to 0.05 wt % sulfur; Metals Content,preferably Vanadium: less than about 50 ppmw; and Nickel: less thanabout 50 ppmw; reduced Asphaltene Content, preferably to less than 10 wt%; reduced micro carbon residue (MCR) content of 5-20% wt and reducedNitrogen Content: in the range from about 0.0-0.7 wt.

Because of the present invention, refiners will realize multipleeconomic and logistical benefits, including: no need to alter orrebalance the refinery operations and product streams in an effort tomeet a new market demand for low sulfur or ultralow sulfur HMFO; insteadto the otherwise previously low value high sulfur HMFO is transformedinto a feedstock suitable for use in subsequent refinery process, morespecifically in anode grade cokers and as feedstock into a fluidcatalytic cracker. No additional units are needed in the refinery withadditional hydrogen or sulfur capacity because the illustrative processcan be conducted as a stand-alone unit; refinery operations can remainfocused on those products that create the greatest value from the crudeoil received (i.e. production of petrochemicals, gasoline and distillate(diesel); refiners can continue using the existing slates of crude oilswithout having to switch to sweeter or lighter crudes to meet theenvironmental requirements for HMFO products.

Production Plant Description: Turning now to a more detailedillustrative embodiment of a production plant, FIG. 2 shows a schematicfor a production plant implementing the process described above fortransforming a Feedstock HMFO to produce a Product HMFO according to thesecond illustrative embodiment. One of skill in the art will appreciatethat FIG. 2 is a generalized schematic drawing, and the exact layout andconfiguration of a plant will depend upon factors such as location,production capacity, environmental conditions (i.e. wind load, etc.) andother factors and elements that a skilled detailed engineering firm willbe able to provide. Such variations are contemplated and within thescope of the present disclosure.

In FIG. 2 , Feedstock HMFO (A) is fed from outside the battery limits(OSBL) to the Oil Feed Surge Drum (1) that receives feed from outsidethe battery limits (OSBL) and provides surge volume adequate to ensuresmooth operation of the unit. Water entrained in the feed and bulksolids (sand, rust particles, etc.) are removed from the HMFO with thewater and bulk solids being discharged a stream (1 c) for treatmentOSBL.

The Feedstock HMFO (A) is withdrawn from the Oil Feed Surge Drum (1) vialine (1 b) by the Oil Feed Pump (3) and is pressurized to a pressurerequired for the process. The pressurized HMFO (A′) then passes throughline (3 a) to the Oil Feed/Product Heat Exchanger (5) where thepressurized HMFO Feed (A′) is partially heated by the Product HMFO (B).The pressurized Feedstock HMFO (A′) passing through line (5 a) isfurther heated against the effluent from the Reactor System (E) in theReactor Feed/Effluent Heat Exchanger (7).

The heated and pressurized Feedstock HMFO (A″) in line (7 a) is thenmixed with Activating Gas (C) provided via line (23 c) at Mixing Point(X) to form a Feedstock Mixture (D). The mixing point (X) can be anywell know gas/liquid mixing system or entrainment mechanism well knownto one skilled in the art.

The Feedstock Mixture (D) passes through line (9 a) to the Reactor FeedFurnace (9) where the Feedstock Mixture (D) is heated to the specifiedprocess temperature. The Reactor Feed Furnace (9) may be a fired heaterfurnace or any other kind to type of heater as known to one of skill inthe art if it will raise the temperature of the Feedstock Mixture (D) tothe desired temperature for the process conditions.

The fully heated Feedstock Mixture (D′) exits the Reactor Feed Furnace(9) via line 9 b and is fed into the Reactor System (11). The fullyheated Feedstock Mixture (D′) enters the Reactor System (11) whereenvironmental contaminates, such a sulfur, nitrogen, and metals arepreferentially removed from the Feedstock HMFO component of the fullyheated Feedstock Mixture. The Reactor System contains a catalyst whichpreferentially removes the sulfur compounds in the Feedstock HMFOcomponent by reacting them with hydrogen in the Activating Gas to formhydrogen sulfide. The Reactor System will also achieve demetallization,denitrogenation, and a certain amount of ring opening hydrogenation ofthe complex aromatics and asphaltenes, however minimal hydrocracking ofhydrocarbons should take place. The process conditions of hydrogenpartial pressure, reaction pressure, temperature and residence time asmeasured by liquid hourly velocity are optimized to achieve desiredfinal product quality. A more detailed discussion of the Reactor System,the catalyst, the process conditions, and other aspects of the processare contained below in the “Reactor System Description.”

The Reactor System Effluent (E) exits the Reactor System (11) via line(11 a) and exchanges heat against the pressurized and partially heatsthe Feedstock HMFO (A′) in the Reactor Feed/Effluent Exchanger (7). Thepartially cooled Reactor System Effluent (E′) then flows via line (11 c)to the Hot Separator (13).

The Hot Separator (13) separates the gaseous components of the ReactorSystem Effluent (F) which are directed to line (13 a) from the liquidcomponents of the Reactor System effluent (G) which are directed to line(13 b). The gaseous components of the Reactor System effluent in line(13 a) are cooled against air in the Hot Separator Vapor Air Cooler (15)and then flow via line (15 a) to the Cold Separator (17).

The Cold Separator (17) further separates any remaining gaseouscomponents from the liquid components in the cooled gaseous componentsof the Reactor System Effluent (F′). The gaseous components from theCold Separator (F″) are directed to line (17 a) and fed onto the AmineAbsorber (21). The Cold Separator (17) also separates any remaining ColdSeparator hydrocarbon liquids (H) in line (17 b) from any Cold Separatorcondensed liquid water (I). The Cold Separator condensed liquid water(I) is sent OSBL via line (17 c) for treatment.

The hydrocarbon liquid components of the Reactor System effluent fromthe Hot Separator (G) in line (13 b) and the Cold Separator hydrocarbonliquids (H) in line (17 b) are combined and are fed to the Oil ProductStripper System (19). The Oil Product Stripper System (19) removes anyresidual hydrogen and hydrogen sulfide from the Product HMFO (B) whichis discharged in line (19 b) to storage OSBL. It is also contemplatedthat a second draw (not shown) may be included to withdraw a distillateproduct, preferably a middle to heavy distillate. The vent stream (M)from the Oil Product Stripper in line (19 a) may be sent to the fuel gassystem or to the flare system that are OSBL. A more detailed discussionof the Oil Product Stripper System is contained in the “Oil ProductStripper System Description.”

The gaseous components from the Cold Separator (F″) in line (17 a)contain a mixture of hydrogen, hydrogen sulfide and light hydrocarbons(mostly methane and ethane). This vapor stream (17 a) feeds an AmineAbsorber System (21) where it is contacted against Lean Amine (J)provided OSBL via line (21 a) to the Amine Absorber System (21) toremove hydrogen sulfide from the gases making up the Activating Gasrecycle stream (C′). Rich amine (K) which has absorbed hydrogen sulfideexits the bottom of the Amine Absorber System (21) and is sent OSBL vialine (21 b) for amine regeneration and sulfur recovery.

The Amine Absorber System overhead vapor in line (21 c) is preferablyrecycled to the process as a Recycle Activating Gas (C′) via the RecycleCompressor (23) and line (23 a) where it is mixed with the MakeupActivating Gas (C″) provided OSBL by line (23 b). This mixture ofRecycle Activating Gas (C′) and Makeup Activating Gas (C″) to form theActivating Gas (C) utilized in the process via line (23 c) as notedabove. A Scrubbed Purge Gas stream (H) is taken from the Amine AbsorberSystem overhead vapor line (21 c) and sent via line (21 d) to OSBL toprevent the buildup of light hydrocarbons or other non-condensablehydrocarbons. A more detailed discussion of the Amine Absorber System iscontained in the “Amine Absorber System Description.”

Reactor System Description: The core process Reactor System (11)illustrated in FIG. 2 comprises a single reactor vessel loaded with theprocess catalyst and sufficient controls, valves and sensors as one ofskill in the art would readily appreciate. One of skill in the art willappreciate that the reactor vessel itself must be engineered towithstand the pressures, temperatures and other conditions (i.e.presence of hydrogen and hydrogen sulfide) of the process. Using specialalloys of stainless steel and other materials typical of such a unit arewithin the skill of one in the art and well known. As illustrated, fixedbed reactors are preferred as these are easier to operate and maintain,however other reactor types are also within the scope of the invention.

A description of the process catalyst, the selection of the processcatalyst and the loading and grading of the catalyst within the reactorvessel is contained in the “Catalyst in Reactor System”.

Alternative configurations for the core process Reactor System (11) arecontemplated. In one illustrative configuration, more than one reactorvessel may be utilized in parallel as shown in FIG. 3 to replace thecore process Reactor System (11) illustrated in FIG. 2 .

In the embodiment shown in FIG. 3 , each reactor vessel is loaded withprocess catalyst in a similar manner and each reactor vessel in theReactor System is provided the heated Feed Mixture (D′) via a commonline 9 b. The effluent from each reactor vessel in the Reactor System isrecombined and forms a combined Reactor Effluent (E) for furtherprocessing as described above via line 11 a. The illustrated arrangementwill allow the three reactors to carry out the process effectivelymultiplying the hydraulic capacity of the overall Reactor System.Control valves and isolation valves may also prevent feed from enteringone reactor vessel but not another reactor vessel. In this way onereactor can be by-passed and placed off-line for maintenance andreloading of catalyst while the remaining reactors continues to receiveheated Feedstock Mixture (D′). It will be appreciated by one of skill inthe art this arrangement of reactor vessels in parallel is not limitedin number to three, but multiple additional reactor vessels can be addedas shown by dashed line reactor. The only limitation to the number ofparallel reactor vessels is plot spacing and the ability to provideheated Feedstock Mixture (D′) to each active reactor.

A cascading series as shown in FIG. 4 can also be substituted for thesingle reactor vessel Reactor System 11 in FIG. 2 . The cascadingreactor vessels are loaded with process catalyst with the same ordifferent activities toward metals, sulfur or other environmentalcontaminates to be removed. For example, one reactor may be loaded witha highly active demetallization catalyst, a second subsequent ordownstream reactor may be loaded with a balanceddemetallization/desulfurizing catalyst, and reactor downstream from thesecond reactor may be loaded with a highly active desulfurizationcatalyst. This allows for greater control and balance in processconditions (temperature, pressure, space flow velocity, etc. . . . ) soit is tailored for each catalyst. In this way one can optimize theparameters in each reactor depending upon the material being fed to thatspecific reactor/catalyst combination and minimize the hydrocrackingreactions.

An alternative implementation of the parallel reactor concept isillustrated in greater detail in FIG. 5 . Heated Feed Mixture isprovided to the reactor System via line 9 b and is distributed amongstmultiple reactor vessels (11, 12 a, 12 b, 12 c and 12 d). Flow of heatedFeedstock to each reactor vessel is controlled by reactor inlet valves(60, 60 a, 60 b, 60 c, and 60 d) associated with each reactor vesselrespectively. Reactor Effluent from each reactor vessel is controlled bya reactor outlet valve (62, 62 a, 62 b, 62 c and 62 d) respectively.Line 9 b has multiple inflow diversion control valves (68, 68 a, 68 band 68 c), the function and role of which will be described below. Line11 a serves to connect the outlet of each reactor, and like Line 9 b hasmultiple outflow diversion control valves (70, 70 a, 70 b and 70 c) thefunction and role of which will be described below. Also shown is aby-pass line defined by lower by-pass control valve (64 64 a, 64 b, 64c) and upper by-pass control valve (66, 66 a, 66 b and 66 c), betweenline 9 b and line 11 a the function and purpose of which will bedescribed below.

One of skill in the art upon careful review of the illustratedconfiguration will appreciate that multiple flow schemes andconfigurations can be achieved with the illustrated arrangement ofreactor vessels, control valves and interconnected lines forming thereactor System. For example, in one configuration one can: open all ofinflow diversion control valves (68, 68 a, 68 b and 68 c); open all ofthe reactor inlet valves (60, 60 a, 60 b, 60 c, and 60 d); open all ofthe reactor outlet valves 62, 62 a, 62 b, 62 c and 62 d; open all of theoutflow diversion control valves (70, 70 a, 70 b and 70 c); and closelower by-pass control valve (64 64 a, 64 b, 64 c) and upper by-passcontrol valve (66, 66 a, 66 b and 66 c), to substantially achieve areactor configuration of five parallel reactors each receiving fullyheated Feedstock from line 9 b and discharging Reactor Effluent intoline 11 a. In such a configuration, all of the reactors are loaded withcatalyst in substantially the same manner. One of skill in the art willalso appreciate that closing of an individual reactor inlet valve andcorresponding reactor outlet valve (for example closing reactor inletvale 60 and closing reactor outlet valve 62) effectively isolates thereactor vessel 11. This will allow for the isolated reactor vessel 11 tobe brought off line and serviced and or reloaded with catalyst while theremaining reactors continue to transform Feedstock HMFO into ProductHMFO.

A second illustrative configuration of the control valves allows for thereactors to work in series as shown in FIG. 4 by using the by-passlines. In such an illustrative embodiment, inflow diversion controlvalve 68 is closed and reactor inlet valve 60 is open. Reactor 11 isloaded with demetallization catalyst and the effluent from the reactorexits via open outlet control valve 62. The closing of outflow diversioncontrol valve 70, the opening of lower by-pass control valve 64 andupper by-pass control valve 66, the opening of reactor inlet valve 60 aand closing of inflow diversion control valve 68 a re-routes theeffluent from reactor 11 to become the feed for reactor 12 a. reactor 12a may be loaded with additional demetallization catalyst, or atransition catalyst loading or a desulfurization catalyst loading. Oneof skill in the art will quickly realize and appreciate that thisconfiguration can be extended to the other reactors 12 b, 12 c and 12 d,thus allowing for a wide range of flow configurations and flow patternsthrough the Reactor Section. As previously noted, an advantage of thisillustrative embodiment of the Reactor Section is that it allows for anyone reactor to be taken off-line, serviced and brought back on linewithout disrupting the transformation of Feedstock HMFO to Product HMFO.It will also allow a plant to adjust its configuration so that as thecomposition of the feedstock HMFO changes, the reactor configuration(number of stages) and catalyst types can be adjusted. For example ahigh metal containing Feedstock, such as a Ural residual based HMFO, mayrequire two or three reactors (i.e. reactors 11, 12 a and 12 b) loadedwith demetallization catalyst and working in series while reactor 12 cis loaded with transition catalyst and reactor 12 d is loaded withdesulfurization catalyst. A large number of permutations and variationscan be achieved by opening and closing control valves as needed andadjusting the catalyst loadings in each of the reactor vessels by one ofskill in the art and only for the sake of brevity need not be describedin detail.

Another illustrative embodiment of the replacement of the single reactorvessel Reactor System 11 in FIG. 2 is a matrix of reactors composed ofinterconnected reactors in parallel and in series. A simple 2×2 matrixarrangement of reactors with associated control valves and piping isshown in FIG. 6 , however a wide variety of matrix configurations suchas 2×3; 3×3, etc. . . . are contemplated and within the scope of thepresent invention. As depicted in FIG. 6 , a 2 reactor by 2 reactor(2×2) matrix of comprises four reactor vessels (11, 12 a, 14 and 14 b)each with reactor inlet control valves (60, 60 a, 76, and 76 a) andreactor outlet control valves (62, 62 a, 78 and 78 a) associated witheach vessel. Horizontal flow control valves (68, 68 a, 70, 70 a, 70 b,74, 74 a, 74 b, 80, 80 a, and 80 b) regulate the flow across the matrixfrom heated Feedstock (D′) in line 9 b to discharging Reactor Effluent(E) into line 11 a. Vertical flow control valves (64, 64 a, 66, 66 a,72, 72 a, 72 b, 72 c, 82, 82 a, 84, and 84 b) control the flow throughthe matrix from line 9 b to line 11 a. One of skill in the art willquickly realize and appreciate that by opening and closing the valvesand varying the catalyst loads present in each reactor, a large numberof configurations may be achieved. One such configuration would be toopen valves numbered: 60, 62, 72, 76, 78, 80, 82, 84, 72 a, 64, 66, 68a, 60 a, 62 a, 72 b, 76 a, 78 a, and 80 b, with all other valves closedsuch that the flow for Feedstock will pass through reactors 11, 14, 12 aand 14 a in series. Another such configuration would be to open valvesnumbered: 60, 62, 70, 64, 66, 68 a, 60 a, 62 a, 72 b, 76 a, 78 a, and 80b, with all other valves closed such that the flow of Feedstock willpass through reactors 11, 12 a and 14 a (but not 14). As with the priorexample, the nature of the Feedstock and the catalyst loaded in eachreactor may be optimized and adjusted to achieve the desired ProductHSFO properties, however for brevity of disclose all such variationswill be apparent to one of skill in the art.

One of the benefits of having a multi-reactor Reactor System is that itallows for a reactor that is experiencing decreased activity or pluggingas a result of coke formation to be isolated and taken off line forturn-around (i.e. deactivated, catalyst and internals replaced, etc. . .. ) without the entire plant having to shut down. Another benefit asnoted above is that it allows one to vary the catalyst loading in theReactor System so that the overall process can be optimized for aspecific feedstock. A further benefit is that one can design the piping,pumps, heaters/heat exchangers, etc. . . . to have excess capacity sothat when an increase in capacity is desired, additional reactors can bequickly brought on-line. Conversely, it allows an operator to takecapacity off line, or turn down a plant output without having a concernabout turn down and minimum flow through a reactor.

Catalyst in Reactor System: The reactor vessel in each Reactor System isloaded with one or more process catalysts. The exact design of theprocess catalyst system is a function of feedstock properties, productrequirements and operating constraints and optimization of the processcatalyst can be carried out by routine trial and error by one ofordinary skill in the art.

The process catalyst(s) comprise at least one metal selected from thegroup consisting of the metals each belonging to the groups 6, 8, 9 and10 of the Periodic Table, and more preferably a mixed transition metalcatalyst such as Ni—Mo, Co—Mo, Ni—W or Ni—Co—Mo are utilized. The metalis preferably supported on a porous inorganic oxide catalyst carrier.The porous inorganic oxide catalyst carrier is at least one carrierselected from the group consisting of alumina, alumina/boria carrier, acarrier containing metal-containing aluminosilicate, alumina/phosphoruscarrier, alumina/alkaline earth metal compound carrier, alumina/titaniacarrier and alumina/zirconia carrier. The preferred porous inorganicoxide catalyst carrier is alumina. The pore size and metal loadings onthe carrier may be systematically varied and tested with the desiredfeedstock and process conditions to optimize the properties of theProduct HMFO. One of skill in the art knows that demetallization using atransition metal catalyst (such a CoMO or NiMo) is favored by catalystswith a relatively large surface pore diameter and desulfurization isfavored by supports having a relatively small pore diameter. Generallythe surface area for the catalyst material ranges from 200-300 m²/g. Thesystematic adjustment of pore size and surface area, and transitionmetal loadings activities to preferentially form a demetallizationcatalyst or a desulfurization catalyst are well known and routine to oneof skill in the art. Catalyst in the fixed bed reactor(s) may bedense-loaded or sock-loaded and the inclusion of inert materials (suchas glass or ceric balls) may be needed to ensure the desired porosity.

The catalyst selection utilized within and for loading the ReactorSystem may be preferential to desulfurization by designing a catalystloading scheme that results in the Feedstock mixture first contacting acatalyst bed that with a catalyst preferential to demetallizationfollowed downstream by a bed of catalyst with mixed activity fordemetallization and desulfurization followed downstream by a catalystbed with high desulfurization activity. In effect the first bed withhigh demetallization activity acts as a guard bed for thedesulfurization bed.

The objective of the Reactor System is to treat the Feedstock HMFO atthe severity required to meet the Product HMFO specification.Demetallization, denitrogenation and hydrocarbon hydrogenation reactionsmay also occur to some extent when the process conditions are optimizedso the performance of the Reactor System achieves the required level ofdesulfurization. Hydrocracking is preferably minimized to reduce thevolume of hydrocarbons formed as by-product hydrocarbons to the process.The objective of the process is to selectively remove the environmentalcontaminates from Feedstock HMFO and minimize the formation ofunnecessary by-product hydrocarbons (C1-C8 hydrocarbons).

The process conditions in each reactor vessel will depend upon thefeedstock, the catalyst utilized and the desired properties of theProduct HMFO. Variations in conditions are to be expected by one ofordinary skill in the art and these may be determined by pilot planttesting and systematic optimization of the process. With this in mind ithas been found that the operating pressure, the indicated operatingtemperature, the ratio of the Activating Gas to Feedstock HMFO, thepartial pressure of hydrogen in the Activating Gas and the spacevelocity all are important parameters to consider. The operatingpressure of the Reactor System should be in the range of 250 psig and3000 psig, preferably between 1000 psig and 2500 psig and morepreferably between 1500 psig and 2200 psig. The indicated operatingtemperature of the Reactor System should be 500° F. to 900° F.,preferably between 650° F. and 850° F. and more preferably between 680°F. and 800° F. The ratio of the quantity of the Activating Gas to thequantity of Feedstock HMFO should be in the range of 250 scf gas/bbl ofFeedstock HMFO to 10,000 scf gas/bbl of Feedstock HMFO, preferablybetween 2000 scf gas/bbl of Feedstock HMFO to 5000 scf gas/bbl ofFeedstock HMFO and more preferably between 2500 scf gas/bbl of FeedstockHMFO to 4500 scf gas/bbl of Feedstock HMFO. The Activating Gas should beselected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseouswater, and methane, so Activating Gas has an ideal gas partial pressureof hydrogen (p_(H2)) greater than 80% of the total pressure of theActivating Gas mixture (P) and preferably wherein the Activating Gas hasan ideal gas partial pressure of hydrogen (p_(H2)) greater than 90% ofthe total pressure of the Activating Gas mixture (P). The Activating Gasmay have a hydrogen mole fraction in the range between 80% of the totalmoles of Activating Gas mixture and more preferably wherein theActivating Gas has a hydrogen mole fraction between 80% and 100% of thetotal moles of Activating Gas mixture. The liquid hourly space velocitywithin the Reactor System should be between 0.05 oil/hour/m³ catalystand 1.0 oil/hour/m³ catalyst; preferably between 0.08 oil/hour/m³catalyst and 0.5 oil/hour/m³ catalyst and more preferably between 0.1oil/hour/m³ catalyst and 0.3 oil/hour/m³ catalyst to achieve deepdesulfurization with product sulfur levels below 0.1 ppmw.

The hydraulic capacity rate of the Reactor System should be between 100bbl of Feedstock HMFO/day and 100,000 bbl of Feedstock HMFO/day,preferably between 1000 bbl of Feedstock HMFO/day and 60,000 bbl ofFeedstock HMFO/day, more preferably between 5,000 bbl of FeedstockHMFO/day and 45,000 bbl of Feedstock HMFO/day, and even more preferablybetween 10,000 bbl of Feedstock HMFO/day and 30,000 bbl of FeedstockHMFO/day. The desired hydraulic capacity may be achieved in a singlereactor vessel Reactor System or in a multiple reactor vessel ReactorSystem as described.

Oil Product Stripper System Description: The Oil Product Stripper System(19) comprises a stripper column (also known as a distillation column orexchange column) and ancillary equipment including internal elements andutilities required to remove hydrogen, hydrogen sulfide and lighthydrocarbons lighter than diesel from the Product HMFO. Such systems arewell known to one of skill in the art, see U.S. Pat. No. 6,640,161;5,709,780; 5,755,933; 4,186,159; 3,314,879 3,844,898; 4,681,661; or3,619,377 the contents of which are incorporated herein by reference, ageneralized functional description is provided herein. Liquid from theHot Separator (13) and Cold Separator (7) feed the Oil Product StripperColumn (19). Stripping of hydrogen and hydrogen sulfide and lighthydrocarbons lighter than diesel may be achieved via a reboiler, livesteam or other stripping medium. The Oil Product Stripper System (19)may be designed with an overhead system comprising an overheadcondenser, reflux drum and reflux pump or it may be designed without anoverhead system. The conditions of the Oil Product Stripper may beoptimized to control the bulk properties of the Product HMFO, morespecifically viscosity and density. It is also contemplated that asecond draw (not shown) may be included to withdraw a distillateproduct, preferably a middle to heavy distillate.

Amine Absorber System Description: The Amine Absorber System (21)comprises a gas liquid contacting column and ancillary equipment andutilities required to remove sour gas (i.e. hydrogen sulfide) from theCold Separator vapor feed so the resulting scrubbed gas can be recycledand used as Activating Gas. Because such systems are well known to oneof skill in the art, see U.S. Pat. Nos. 4,425,317; 4,085,199; 4,080,424;4,001,386; which are incorporated herein by reference, a generalizedfunctional description is provided herein. Vapors from the ColdSeparator (17) feed the contacting column/system (19). Lean Amine (orother suitable sour gas stripping fluids or systems) provided from OSBLis utilized to scrub the Cold Separator vapor so hydrogen sulfide iseffectively removed. The Amine Absorber System (19) may be designed witha gas drying system to remove the any water vapor entrained into theRecycle Activating Gas (C′). The absorbed hydrogen sulfide is processedusing conventional means OSBL in a tail gas treating unit, such as aClaus combustion sulfur recovery unit or sulfur recovery system thatgenerates sulfuric acid.

The following examples will provide one skilled in the art with a morespecific illustrative embodiment for conducting the process disclosedand claimed herein:

Example 1

Overview: The purpose of a pilot test run is to demonstrate thatfeedstock HMFO can be processed through a reactor loaded withcommercially available catalysts at specified conditions to removeenvironmental contaminates, specifically sulfur and other contaminantsfrom the HMFO to produce a product HMFO that is MARPOL compliant, thatis production of a Low Sulfur Heavy Marine Fuel Oil (LS-HMFO) orUltra-Low Sulfur Heavy Marine Fuel Oil (USL-HMFO).

Pilot Unit Set Up: The pilot unit will be set up with two 434 cm³reactors arranged in series to process the feedstock HMFO. The leadreactor will be loaded with a blend of a commercially availablehydrodemetallization (HDM) catalyst and a commercially availablehydro-transition (HDT) catalyst. One of skill in the art will appreciatethat the HDT catalyst layer may be formed and optimized using a mixtureof HDM and HDS catalysts combined with an inert material to achieve thedesired intermediate/transition activity levels. The second reactor willbe loaded with a blend of the commercially available hydro-transition(HDT) and a commercially available hydrodesulfurization (HDS).Alternatively, one can load the second reactor simply with acommercially hydrodesulfurization (HDS) catalyst. One of skill in theart will appreciate that the specific feed properties of the FeedstockHMFO may affect the proportion of HDM, HDT and HDS catalysts in thereactor system. A systematic process of testing different combinationswith the same feed will yield the optimized catalyst combination for anyfeedstock and reaction conditions. For this example, the first reactorwill be loaded with ⅔ hydrodemetallization catalyst and ⅓hydro-transition catalyst. The second reactor will be loaded with allhydrodesulfurization catalyst. The catalysts in each reactor will bemixed with glass beads (approximately 50% by volume) to improve liquiddistribution and better control reactor temperature. For this pilot testrun, one should use these commercially available catalysts: HDM:Albemarle KFR 20 series or equivalent; HDT: Albemarle KFR 30 series orequivalent; HDS: Albemarle KFR 50 or KFR 70 or equivalent. Once set upof the pilot unit is complete, the catalyst can be activated bysulfiding the catalyst using dimethyldisulfide (DMDS) in a manner wellknown to one of skill in the art.

Pilot Unit Operation: Upon completion of the activating step, the pilotunit will be ready to receive the feedstock HMFO and Activating Gasfeed. For the present example, the Activating Gas can be technical gradeor better hydrogen gas. The mixed Feedstock HMFO and Activating Gas willbe provided to the pilot plant at rates and operating conditions asspecified: Oil Feed Rate: 108.5 ml/h (space velocity=0.25/h);Hydrogen/Oil Ratio: 570 Nm3/m3 (3200 scf/bbl); Reactor Temperature: 372°C. (702° F.); Reactor Outlet Pressure: 13.8 MPa(g) (2000 psig).

One of skill in the art will know that the rates and conditions may besystematically adjusted and optimized depending upon feed properties toachieve the desired product requirements. The unit will be brought to asteady state for each condition and full samples taken so analyticaltests can be completed. Material balance for each condition should beclosed before moving to the next condition.

Expected impacts on the Feedstock HMFO properties are: Sulfur Content(wt %): Reduced by at least 80%; Metals Content (wt %): Reduced by atleast 80%; MCR/Asphaltene Content (wt %): Reduced by at least 30%;Nitrogen Content (wt %): Reduced by at least 20%; C1-Naphtha Yield (wt%): Not over 3.0% and preferably not over 1.0%.

Process conditions in the Pilot Unit can be systematically adjusted asper Table 4 to assess the impact of process conditions and optimize theperformance of the process for the specific catalyst and feedstock HMFOutilized.

TABLE 4 Optimization of Process Conditions HC Feed Rate (ml/h), Nm³H₂/m³ oil/ Temp Pressure Case [LHSV(/h)] scf H₂/bbl oil (° C./° F.) (MPa(g)/psig) Baseline 108.5 [0.25] 570/3200 372/702 13.8/2000 T1 108.5[0.25] 570/3200 362/684 13.8/2000 T2 108.5 [0.25] 570/3200 382/72013.8/2000 L1 130.2 [0.30] 570/3200 372/702 13.8/2000 L2  86.8 [0.20]570/3200 372/702 13.8/2000 H1 108.5 [0.25] 500/2810 372/702 13.8/2000 H2108.5 [0.25] 640/3590 372/702 13.8/2000 S1  65.1 [0.15] 620/3480 385/72515.2/2200

In this way, the conditions of the pilot unit can be optimized toachieve less than 0.5% wt. sulfur product HMFO and preferably a 0.1% wt.sulfur product HMFO. Conditions for producing ULS-HMFO (i.e. 0.1% wt.sulfur product HMFO) will be: Feedstock HMFO Feed Rate: 65.1 ml/h (spacevelocity=0.15/h); Hydrogen/Oil Ratio: 620 Nm³/m³ (3480 scf/bbl); ReactorTemperature: 385° C. (725° F.); Reactor Outlet Pressure: 15 MPa(g) (2200psig)

Table 5 summarizes the anticipated impacts on key properties of HMFO.

TABLE 5 Expected Impact of Process on Key Properties of HMFO PropertyMinimum Typical Maximum Sulfur Conversion/Removal 80% 90% 98% MetalsConversion/Removal 80% 90% 100%  MCR Reduction 30% 50% 70% AsphalteneReduction 30% 50% 70% Nitrogen Conversion 10% 30% 70% C1 through NaphthaYield 0.5%  1.0%  4.0%  Hydrogen Consumption (scf/bbl) 500 750 1500

Table 6 lists analytical tests to be carried out for thecharacterization of the Feedstock HMFO and Product HMFO. The analyticaltests include those required by ISO for the Feedstock HMFO and theproduct HMFO to qualify and trade in commerce as ISO compliant residualmarine fuels. The additional parameters are provided so that one skilledin the art will be able to understand and appreciate the effectivenessof the inventive process.

TABLE 6 Analytical Tests and Testing Procedures Sulfur Content ISO 8754or ISO 14596 or ASTM D4294 Density @ 15° C. ISO 3675 or ISO 12185Kinematic Viscosity @ 50° C. ISO 3104 Pour Point, ° C. ISO 3016 FlashPoint, ° C. ISO 2719 CCAI ISO 8217, ANNEX B Ash Content ISO 6245 TotalSediment - Aged ISO 10307-2 Micro Carbon Residue, mass % ISO 10370 H2S,mg/kg IP 570 Acid Number ASTM D664 Water ISO 3733 Specific ContaminantsIP 501 or IP 470 (unless indicated otherwise) Vanadium or ISO 14597Sodium Aluminum or ISO 10478 Silicon or ISO 10478 Calcium or IP 500 Zincor IP 500 Phosphorous IP 500 Nickle Iron Distillation ASTM D7169 C:HRatio ASTM D3178 SARA Analysis ASTM D2007 Asphaltenes, wt % ASTM D6560Total Nitrogen ASTM D5762 Vent Gas Component Analysis FID GasChromatography or comparable

Table 7 contains the Feedstock HMFO analytical test results and theProduct HMFO analytical test results expected from the inventive processthat indicate the production of a LS HMFO. It will be noted by one ofskill in the art that under the conditions, the levels of hydrocarboncracking will be minimized to levels substantially lower than 10%, morepreferably less than 5% and even more preferably less than 1% of thetotal mass balance.

TABLE 7 Analytical Results Feedstock Product HMFO HMFO Sulfur Content,mass % 3.0   0.3 Density @ 15° C., kg/m³ 990  950 ⁽¹⁾ KinematicViscosity @ 50° C., mm²/s 380  100 ⁽¹⁾ Pour Point, ° C. 20  10 FlashPoint, ° C. 110  100 ⁽¹⁾ CCAI 850  820 Ash Content, mass % 0.1   0.0Total Sediment - Aged, mass % 0.1   0.0 Micro Carbon Residue, mass %13.0   6.5 H2S, mg/kg 0   0 Acid Number, mg KO/g 1   0.5 Water, vol %0.5   0 Specific Contaminants, mg/kg Vanadium 180  20 Sodium 30   1Aluminum 10   1 Silicon 30   3 Calcium 15   1 Zinc 7   1 Phosphorous 2  0 Nickle 40   5 Iron 20   2 Distillation, ° C./° F. IBP 160/320120/248  5% wt 235/455 225/437 10% wt 290/554 270/518 30% wt 410/770370/698 50% wt 540/1004 470/878 70% wt 650/1202 580/1076 90% wt 735/1355660/1220 FBP 820/1508 730/1346 C:H Ratio (ASTM D3178) 1.2   1.3 SARAAnalysis Saturates 16  22 Aromatics 50  50 Resins 28  25 Asphaltenes 6  3 Asphaltenes, wt % 6.0   2.5 Total Nitrogen, mg/kg 4000 3000 Note:⁽¹⁾ It is expected that property will be adjusted to a higher vaue bypost process removal of light material via distillation or strippingfrom product HMFO.

The product HMFO produced by the inventive process will reach ULS HMFOlimits (i.e. 0.1% wt. sulfur product HMFO) by systematic variation ofthe process parameters, for example by a lower space velocity or byusing a Feedstock HMFO with a lower initial sulfur content. Theresulting product will make a ideal feedstock for anode or needlecoking.

Example 2: RMG-380 HMFO

Pilot Unit Set Up: A pilot unit was set up as noted above in Example 1with the following changes: the first reactor was loaded with: as thefirst (upper) layer encountered by the feedstock 70% vol Albemarle KFR20 series hydrodemetallization catalyst and 30% vol Albemarle KFR 30series hydro-transition catalyst as the second (lower) layer. The secondreactor was loaded with 20% Albemarle KFR 30 series hydrotransitioncatalyst as the first (upper) layer and 80% vol hydrodesulfurizationcatalyst as the second (lower) layer. The catalyst was activated bysulfiding the catalyst with dimethyldisulfide (DMDS) in a manner wellknown to one of skill in the art.

Pilot Unit Operation: Upon completion of the activating step, the pilotunit was ready to receive the feedstock HMFO and Activating Gas feed.The Activating Gas was technical grade or better hydrogen gas. TheFeedstock HMFO was a commercially available and merchantable ISO 8217(2017) compliant HMFO, except for a high sulfur content (2.9 wt %). Themixed Feedstock HMFO and Activating Gas was provided to the pilot plantat rates and conditions as specified in Table 8 below. The conditionswere varied to optimize the level of sulfur in the product HMFOmaterial.

TABLE 8 Process Conditions Product HC Feed Nm³ H₂/ Pressure HMFO Rate(ml/h), m³ oil/scf Temp (MPa (g)/ Sulfur Case [LHSV(/h)] H₂/bbl oil (°C./° F.) psig) % wt. Baseline 108.5 [0.25] 570/3200 371/700 13.8/20000.24 T1 108.5 [0.25] 570/3200 362/684 13.8/2000 0.53 T2 108.5 [0.25]570/3200 382/720 13.8/2000 0.15 L1 130.2 [0.30] 570/3200 372/70213.8/2000 0.53 S1  65.1 [0.15] 620/3480 385/725 15.2/2200 0.10 P1 108.5[0.25] 570/3200 371/700 /1700 0.56 T2/P1 108.5 [0.25] 570/3200 382/720/1700 0.46

Analytical data for a representative sample of the feedstock HMFO andrepresentative samples of product HMFO are provided below:

TABLE 7 Analytical Results - HMFO (RMG-380) Feedstock Product ProductSulfur Content, mass % 2.9 0.3 0.1 Density @ 15° C., kg/m³ 988 932 927Kinematic Viscosity @ 382 74 47 50° C., mm²/s Pour Point, ° C. −3 −12−30 Flash Point, ° C. 116 96 90 CCAI 850 812 814 Ash Content, mass %0.05 0.0 0.0 Total Sediment - Aged, 0.04 0.0 0.0 mass % Micro CarbonResidue, 11.5 3.3 4.1 mass % H2S, mg/kg 0.6 0 0 Acid Number, mg KO/g 0.30.1 >0.05 Water, vol % 0 0.0 0.0 Specific Contaminants, mg/kg Vanadium138 15 <1 Sodium 25 5 2 Aluminum 21 2 <1 Silicon 16 3 1 Calcium 6 2 <1Zinc 5 <1 <1 Phosphorous <1 2 1 Nickle 33 23 2 Iron 24 8 1 Distillation,° C./° F. IBP 178/352 168/334 161/322  5% wt 258/496 235/455 230/446 10%wt 298/569 270/518 264/507 30% wt 395/743 360/680 351/664 50% wt 517/962461/862 439/822 70% wt  633/1172  572/1062  552/1026 90% wt  >720/>1328 694/1281  679/1254 FBP  >720/>1328  >720/>1328  >720/>1328 C:H Ratio(ASTM 1.2 1.3 1.3 D3178) SARA Analysis Saturates 25.2 28.4 29.4Aromatics 50.2 61.0 62.7 Resins 18.6 6.0 5.8 Asphaltenes 6.0 4.6 2.1Asphaltenes, wt % 6.0 4.6 2.1 Total Nitrogen, mg/kg 3300 1700 1600

As noted above in Table 7, both feedstock HMFO and product HMFOexhibited observed bulk properties consistent with ISO 8217 (2017) for amerchantable residual marine fuel oil, except that the sulfur content ofthe product HMFO was significantly reduced as noted above when comparedto the feedstock HMFO.

One of skill in the art will appreciate that the above product HMFOproduced by the inventive process has achieved not only an ISO 8217(2017) compliant LS HMFO (i.e. 0.5% wt. sulfur) but also an ISO 8217(2017) compliant ULS HMFO limits (i.e. 0.1% wt. sulfur) product HMFO.This material will make an excellent feedstock for needle coking orprocessing in an FCC unit.

Example 3: RMK-500 HMFO

The feedstock to the pilot reactor utilized in example 2 above waschanged to a commercially available and merchantable ISO 8217 (2017)RMK-500 compliant HMFO, except that it has high environmentalcontaminates (i.e. sulfur (3.3 wt %)). Other bulk characteristic of theRMK-500 feedstock high sulfur HMFO are provide below:

TABLE 8 Analytical Results - Feedstock HMFO (RMK-500) Sulfur Content,mass % 3.3 Density @ 15° C., kg/m³ 1006 Kinematic Viscosity @ 50° C.,mm²/s 500

The mixed Feedstock (RMK-500) HMFO and Activating Gas was provided tothe pilot plant at rates and conditions and the resulting sulfur levelsachieved in the table below

TABLE 9 Process Conditions HC Feed Nm³ H₂/ Temp Pressure Product Rate(ml/h), m³ oil/scf (° C. / (MPa (g)/ (RMK-500) Case [LHSV( /h)] H/bbloil ° F.) psig) sulfur % wt. A 108.5 [0.25]  640/3600 377/710 13.8/20000.57 B 95.5 [0.22] 640/3600 390/735 13.8/2000 0.41 C 95.5 [0.22]640/3600 390/735 11.7/1700 0.44 D 95.5 [0.22] 640/3600 393/740 10.3/15000.61 E 95.5 [0.22] 640/3600 393/740 17.2/2500 0.37 F 95.5 [0.22]640/3600 393/740  8.3/1200 0.70 G 95.5 [0.22] 640/3600 416/780  8.3/1200

The resulting product (RMK-500) HMFO exhibited observed bulk propertiesconsistent with the feedstock (RMK-500) HMFO, except that the sulfurcontent was significantly reduced as noted in the above table.

One of skill in the art will appreciate that the above product HMFOproduced by the inventive process has achieved a LS HMFO (i.e. 0.5% wt.sulfur) product HMFO having bulk characteristics of a ISO 8217 (2017)compliant RMK-500 residual fuel oil. It will also be appreciated thatthe process can be successfully carried out under non-hydrocrackingconditions (i.e. lower temperature and pressure) that substantiallyreduce the hydrocracking of the feedstock material. It should be notedthat when conditions were increased to much higher pressure (Example E)a product with a lower sulfur content was achieved, however it wasobserved that there was an increase in light hydrocarbons and wildnaphtha production.

It will be appreciated by those skilled in the art that changes could bemade to the illustrative embodiments described above without departingfrom the broad inventive concepts thereof. It is understood, therefore,that the inventive concepts disclosed are not limited to theillustrative embodiments or examples disclosed, but it is intended tocover modifications within the scope of the inventive concepts asdefined by the claims.

1. A process for treating high sulfur Heavy Marine Fuel Oil for use asfeedstock in a subsequent refinery unit, the process comprising: mixinga quantity of Feedstock Heavy Marine Fuel Oil with a quantity ofActivating Gas mixture to give a Feedstock Mixture; contacting theFeedstock Mixture with one or more catalysts under reactive conditionsto form a Process Mixture from said Feedstock Mixture; receiving saidProcess Mixture and separating the liquid components of the ProcessMixture from the bulk gaseous components of the Process Mixture;subsequently separating any residual gaseous components and by-producthydrocarbon components from the Process Mixture to form a Product HeavyMarine Fuel Oil; and, discharging the Product Heavy Marine Fuel Oil to asubsequent refinery unit.
 2. The process of claim 1 wherein theFeedstock Heavy Marine Fuel Oil complies with ISO 8217 (2017) Table 2 asa residual marine fuel except that it has a sulfur content (ISO 14596 orISO 8754) greater than 0.5% wt and wherein the Product Heavy Marine FuelOil complies with ISO 8217 (2017) Table 2 as a residual marine fuel andhas a sulfur content (ISO 14596 or ISO 8754) between the range of 0.50mass % to 0.05 mass %.
 3. The process of claim 2, further comprisingfractionating the Product Heavy Marine Fuel Oil to remove a light tomiddle distillate fraction, said light to middle distillate fractionhave a maximum boiling point less than 650° F.
 4. The process of claim 2wherein the one or more catalysts comprises: a porous inorganic oxidecatalyst carrier and a transition metal catalyst, wherein the porousinorganic oxide catalyst carrier is at least one carrier selected fromthe group consisting of alumina, alumina/boria carrier, a carriercontaining metal-containing aluminosilicate, alumina/phosphorus carrier,alumina/alkaline earth metal compound carrier, alumina/titania carrierand alumina/zirconia carrier, and wherein the transition metal catalystis one or more metals selected from the group consisting of group 6, 8,9 and 10 of the Periodic Table; and wherein the Activating Gas isselected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseouswater, and methane, such that Activating Gas has an ideal gas partialpressure of hydrogen (p_(H2)) greater than 80% of the total pressure ofthe Activating Gas mixture (P).
 5. The process of claim 4 wherein thereactive conditions comprise: the ratio of the quantity of theActivating Gas to the quantity of Feedstock Heavy Marine Fuel Oil is inthe range of 250 scf gas/bbl of Feedstock Heavy Marine Fuel Oil to10,000 scf gas/bbl of Feedstock Heavy Marine Fuel Oil; a the totalpressure is between of 250 psig and 3000 psig; and, the indicatedtemperature is between of 500° F. to 900° F., and, wherein the liquidhourly space velocity is between 0.05 oil/hour/m³ catalyst and 1.0oil/hour/m³ catalyst.
 6. The process of claim 1 wherein said ProductHeavy Marine Fuel Oil has a maximum sulfur content (ISO 14596 or ISO8754) between the range of 0.01 mass % to 0.5 mass % and the subsequentrefinery process is selected from the group consisting of: anode gradecoking process unit; needle grade coking process unit; and fluidcatalytic cracking process unit.
 7. The process of claim 1 wherein saidProduct Heavy Marine Fuel Oil is a suitable feedstock for anode gradecoking and said Product Heavy Marine Fuel Oil has a sulfur content lessthan about 1.0 wt %; and a vanadium content less than about 100 ppmw andnickel content less than about 100 ppmw.
 8. The process of claim 1wherein said Product Heavy Marine Fuel Oil is a suitable feedstock forneedle grade coking and said Product Heavy Marine Fuel Oil has a sulfurcontent in the range from about 0.01-0.7 wt %; a vanadium content lessthan about 50 ppmw; a nickel content less than about 50 ppmw; anaromatic content in the range from about 50-80 wt %; an asphaltenecontent less than about 8 wt %; a nitrogen content in the range fromabout 0.0-0.7 wt; and an ash value less than about 100 ppmw.
 9. A devicefor the production of a Product Heavy Marine Fuel Oil as a feedstock foruse in a subsequent refinery operation, the device comprising: means formixing a quantity of Feedstock Heavy Marine Fuel Oil with a quantity ofActivating Gas mixture to give a Feedstock Mixture; means for heatingthe Feedstock mixture, wherein the means for mixing and means forheating are in fluid communication with each other; a Reaction System influid communication with the means for heating, wherein the ReactionSystem comprises one or more reactor vessels wherein said reactorvessels contains one or more catalyst materials to promote thetransformation of the Feedstock mixture to a Process Mixture; means forreceiving said Process Mixture and separating the liquid components ofthe Process Mixture from the bulk gaseous components of the ProcessMixture, said means for receiving in fluid communication with thereaction System; and means for separating any residual gaseouscomponents and by-product hydrocarbon components from the ProcessMixture to form a Product Heavy Marine Fuel Oil and means fordischarging the Product Heavy Marine Fuel Oil.
 10. The device of claim 9wherein the Feedstock Heavy Marine Fuel Oil complies with ISO 8217(2017) Table 2 as a residual marine fuel and has a sulfur content (ISO14596 or ISO 8754) between the range of 5.0 mass % to 1.0 mass % andwherein the Product Heavy Marine Fuel Oil complies with ISO 8217 (2017)Table 2 as a residual marine fuel and has a sulfur content (ISO 14596 orISO 8754) between the range of 0.50 mass % to 0.05 mass %.
 11. Thedevice of claim 10 wherein the one or more catalyst materials is aporous inorganic oxide catalyst carrier and a transition metal catalyst,wherein the porous inorganic oxide catalyst carrier is at least onecarrier selected from the group consisting of alumina, alumina/boriacarrier, a carrier containing metal-containing aluminosilicate,alumina/phosphorus carrier, alumina/alkaline earth metal compoundcarrier, alumina/titania carrier and alumina/zirconia carrier, andwherein the transition metal catalyst is one or more metals selectedfrom the group consisting of group 6, 8, 9 and 10 of the Periodic Table.12. A low sulfur feedstock material for a subsequent refinery processconsisting essentially of a hydroprocessed high sulfur heavy marine fueloil, wherein prior to hydroprocessing the high sulfur heavy marine fueloil is compliant with ISO 8217 (2017) as a Table 2 residual marine fuelexcept for having a sulfur content (ISO 14596 or ISO 8754) greater than0.5% wt. and wherein the low sulfur feedstock material exhibitsproperties compliant with ISO 8217 (2017) as a Table 2 residual marinefuel.
 13. The composition of claim 12, wherein the high sulfur heavymarine fuel oil has a sulfur content (ISO 14596 or ISO 8754) in therange from 1.0% wt. to 5.0% wt. and the low sulfur feedstock materialhas a sulfur content (ISO 14596 or ISO 8754) in the range of 0.5% wt.and 0.05% wt.
 14. The composition of claim 13, wherein the low sulfurfeedstock material has a sulfur content (ISO 14596 or ISO 8754) lessthan 0.1 wt %.
 15. The composition of claim 13 wherein low sulfurfeedstock material has a maximum kinematic viscosity at 50° C. (ISO3104) and a density at 15° C. (ISO 3675) resulting in a CCAI is in therange of 780 to 870; a flash point (ISO 2719) no lower than 60.0° C.; atotal sediment—aged (ISO 10307-2) of less than 0.10% wt.; a carbonresidue—micro method (ISO 10370) less than 20.00% wt., and a maximumaluminum plus silicon (ISO 10478) content of 60 mg/kg.
 16. Thecomposition of claim 13 wherein said low sulfur feedstock material is asuitable feedstock for anode grade coking and said low sulfur feedstockmaterial has a vanadium content less than about 100 ppmw and a nickelcontent less than about 100 ppmw.
 17. The composition of claim 14wherein said low sulfur feedstock material is a suitable feedstock forneedle grade coking and said low sulfur feedstock material has a sulfurcontent in the range from about 0.01-0.7 wt %; a vanadium content lessthan about 50 ppmw; a nickel content less than about 50 ppmw; anaromatic content in the range from about 50-80 wt %; an asphaltenecontent less than about 8 wt %; a nitrogen content less than 0.7 wt %;and an ash value less than about 100 ppmw.
 18. The composition of claim14 wherein low sulfur feedstock material is a suitable feedstock for afluid catalytic cracking unit and said low sulfur feedstock material hasa sulfur content in the range of 0.1 to 0.05 wt % sulfur; a vanadiumcontent less than about 50 ppmw; a nickel content less than about 50ppmw; an asphaltene content less than 10 wt %; a micro carbon residue(MCR) content of in the range of 5-20 wt %; and nitrogen content lessthan 0.7 wt %.